EP0013330A1 - Process for preparing reinforced rubber vulcanisates and the articles thus obtained - Google Patents

Process for preparing reinforced rubber vulcanisates and the articles thus obtained Download PDF

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Publication number
EP0013330A1
EP0013330A1 EP79104787A EP79104787A EP0013330A1 EP 0013330 A1 EP0013330 A1 EP 0013330A1 EP 79104787 A EP79104787 A EP 79104787A EP 79104787 A EP79104787 A EP 79104787A EP 0013330 A1 EP0013330 A1 EP 0013330A1
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EP
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Prior art keywords
novolak
phenol
mixtures
rubber
resins
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EP79104787A
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German (de)
French (fr)
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EP0013330B1 (en
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Arnold Dr. Giller
Joachim Weil
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T152/00—Resilient tires and wheels
    • Y10T152/10—Tires, resilient
    • Y10T152/10495—Pneumatic tire or inner tube

Definitions

  • rubber mixtures made of natural or synthetic rubber can be reinforced by adding novlaken and resols in a ratio of 9: 1 to 1: 9.
  • the strengthening of various types of rubber by adding phenol novolaks and hexamethylenetetramine as curing agents is of practical importance.
  • the reinforcing effect of the resins used can optionally be effectively regulated by the amount of the curing agent used.
  • the invention thus relates to a process for the production of reinforced vulcanizates by vulcanization of natural or synthetic rubber mixtures with novolak resins in the presence of an amine compound as the curing agent, which is characterized in that the vulcanization in the presence of reactive melamine resins, such as those obtained by reacting melamine with 0.5 to 6 moles of aldehyde are obtained as hardeners in a proportion of 0.5 to 120, preferably 2 to 50% by weight, based on novolak resin, and that the phenolic component of the novolak from the phenol group is multivalent Multinuclear phenols, alkylphenols, mixtures of alkylphenols with phenol is selected, which may also contain additions of resorcinol, phenylphenol or polyalkylphenols.
  • the additives are incorporated in such an amine compound as the curing agent, which is characterized in that the vulcanization in the presence of reactive melamine resins, such as those obtained by reacting
  • the methylol groups present in the melamine resin can be etherified freely or at least partially by reaction with monohydric alcohols with 1 to 12 carbon atoms.
  • Melamine resins as they can be used according to known methods mentioned above, alone, have the same grip sc h Ungen of various kinds a much weaker effect than the commonly used novolak Hexamethylentetraminsysteme. If solid, reactive melamine resins are used, their effect depends to a large extent on the fineness of their particles. In practice, the particle size of active fillers is only reached in exceptional cases. Solid melamine resins can optionally also be used in the process according to the invention. Usually a melamine resin with a particle size of at most 100 ⁇ m, preferably about 50 ⁇ m will be used. In a dissolved form, highly reactive melamine resins are relatively easy to manufacture.
  • Resins of this type are only suitable for incorporation into rubbers to a limited extent because the required solvents such as higher alcohols, water, polyglycols or esters are not compatible with most types of rubbers. They have to be evaporated in the course of the mixing process. Hexamethoxymethylmelamine itself is good> workable, but hardens slowly. For this reason, it does not have the effect of the phenol novolak / hexamethylenetetramine mixtures used in practice.
  • the rate of resin curing and the curing effect itself by adding suitable mono- or dibasic organic acids with at least 2 and at most 20 C atoms or their anhydrides e.g. B. phthalic acid, benzoic acid, maleic acid, fumaric acid, tri- or pyromellitic acid and their anhydrides or sulfonic acids such as naphthalenedisulfonic acid or sulfanilic acid, are significantly accelerated and intensified.
  • polyester resins made from polycarboxylic acids and polyhydric alcohols with an acid number of 20 and higher, e.g. B. to 100, which can also be modified by monocarboxylic acids and monohydric alcohols.
  • the proportion of monovalent components should not exceed 25 equivalent%, based on the acid or alcohol component.
  • the organic acids or polyester resins used for acceleration can be added in amounts of 0.1 to about 5, preferably 51.5 to 3% by weight, based on rubber; will. Larger or smaller acid doses are quite possible.
  • the hardening can also be accelerated with the aid of strong inorganic acids, such as phosphoric acid or acidic phosphoric acid esters.
  • strong inorganic acids such as phosphoric acid or acidic phosphoric acid esters.
  • this method of operation is less expedient because of the precautionary measures required when handling such acids.
  • the starting mixtures used according to the invention can be produced in the usual way in internal mixers or on mixing rollers.
  • care must be taken to ensure that the mixing temperature in any phase of the Mixing exceeds the melting point of the resins, especially the novolak resins, so that they can be completely distributed.
  • the melamine resins to be used as curing agents are incorporated in such a way that there is no premature self-condensation or premature reaction with the novolak to be cured . This is possible if the melamine resins are incorporated at the end of the mixing process if the temperature is not too high.
  • the temperature depends on the type of melamine resin used, the amount of acid and the time and is generally from 80 ° to 120 ° C. in individual cases it can also be higher - e.g. B. when using hexamethoxymethylmelamine in the absence of an acid - or lower.
  • Suitable types of rubber are, for example, natural rubber, styrene rubber, acrylonitrile rubber, polybutadiene, butyl rubber, ethylene-propylene-diene terpolymer rubber or mixtures thereof, as are usually used in the tire industry or for the production of technical rubber products.
  • Suitable novolak resins are e.g. B. those made of phenol, polyvalent multinuclear phenols such as bisphenols, e.g. B. diphenylolpropane or diphenylolmethane, or mixtures of phenol and alkylphenols, such as tertiary-butylphenol, octylphenol or nonylphenol and aldehydes, preferably formaldehyde in the acidic region.
  • the novolak resins can also contain plasticizing components, such as polyethylene glycols, tall oil or other suitable plasticizers.
  • novolak resins can also be used which consist exclusively of alkylphenols which carry an alkyl group of 1 to 12 carbon atoms; however, these are only of limited use since they are less hardenable.
  • the novolak resins can contain additions of resorcinol or phenylphenol or phenols containing several alkyl groups.
  • novolak resins from phenol and mixtures of phenol and cashew nutshell oil and from phenol and alkylphenols with 4 to 12 carbon atoms in the alkyl part, in particular p-tert-butyl, octyl or nonylphenol.
  • the proportion of substituted phenols in the novolak can vary, although the novolak should still be curable. In general, a proportion of alkylphenol of at most 70 mol% of the total phenol component will be chosen.
  • the proportion of the novolak is generally 1 to 30, preferably 3 to 20% by weight, based on the elastomer. In individual cases, larger quantities, e.g. B. Use 100 and more wt .-%, based on the elastomer. With such a high novolak content, hard products are obtained which differ significantly in their properties from the usual highly elastic rubber vulcanizates.
  • Preferred melamine resins are hexamethoxymethylmelamine or corresponding higher condensed polynuclear products or at least partially etherified trimethylol, tetramethylol or pentamethylol melamine resins.
  • the degree of condensation of the aldehyde, especially formaldehyde resins and their content of free methylol groups can be regulated in the usual way by appropriate adjustment of the reaction medium.
  • the free methylol groups can be etherified with monohydric alcohols having 1 to 12, preferably 1 to 8, carbon atoms, such as methanol, the various butanols, ethylhexyl alcohol, n-octanol, nonanol, dodecyl alcohol.
  • the optimum amounts of melamine resins required for curing the novolak resins must be determined in preliminary tests which are easy to carry out. In general, about 1 to 80, preferably 2 to 50% by weight of melamine resin is required per 100 parts by weight of novolak resin.
  • plasticizers as are customary in rubber processing, for example aromatic polyethers, phthalic acid esters or the like.
  • the commercially available active or inactive carbon blacks, silicas, kaolins, chalk or other customary fillers can also be used as fillers.
  • sulfur is used for vulcanization in connection with the well-known accelerators. In some cases, however, it is also possible to work without sulfur. Vulcanization in the presence of sulfur is preferred. The course of vulcanization can be adapted to practical requirements by selecting suitable accelerators which are customary in rubber technology.
  • Technical rubber articles can be produced from the mixtures produced according to the invention and containing a novolak resin and a melamine resin; but they can also be used for the manufacture of motor vehicle tires.
  • the mixtures V 1 and V 2 are comparative mixtures.
  • Mixture V 2 shows the reinforcement of a styrene-butadiene R USS mixture with a commercially available phenol novolak when cured with hexamethylenetetramine.
  • Mixture 1 shows the reinforcing effect according to the invention when using a commercially available, water- and solvent-free, higher-viscosity hexamethoxymelamine quality.
  • Mixture 2 shows the effect of the benzoic acid used to accelerate curing.
  • the vulcanizates of the mixture V 2 are distinguished from mixture V 1 by a somewhat higher voltage value at 100% and significantly higher vulcanizate hardness.
  • the mixture 1 produced according to the invention gives vulcanizates with a further increased tension value at 100% elongation and significantly higher hardness.
  • benzoic acid By using benzoic acid, the tension values at 100, 200 and 300% elongation and the vulcanizate hardness are additionally increased.
  • vulcanizate hardness over 90 Shore A can be obtained.
  • vulcanizates are obtained which, in their test data, are the vulcanizates largely correspond to mixture 1.
  • Mixtures 3 and 4 produced according to the invention show that plasticizing additives, such as diethylene glycol or an acidic phthalic acid pentaerythritol polyester resin, can be used with advantage.
  • the diethylene glycol reduces the Mooney viscosity by approx. 10-15 units compared to a comparison mixture.
  • the polyester resin with an acid number of approx. 200 added to mixture 4 favors the curing reaction.
  • Tables 2 to 4 used the same rubber and carbon black as in Table 1.
  • Mixtures V5 and V12 are comparative mixtures. As the comparison of the hardness and the tension values of the mixtures 6 to 8 according to the invention in Table 2 shows with the corresponding values of the comparison sample V5, these are Hardness and the voltage values from those of the encryption g l calibration sample increased. Mixtures 9 to 11 show an even greater increase in hardness and tension, which is presumably due to the combined action of the two melamine resins.
  • mixtures 13 and 14 according to the invention also show a significant improvement in hardness and stress value compared to comparative sample V12. The higher hardness is probably due to the other accelerator system.
  • Table 4 shows an increased vulcanizate with good tension values and high hardness in both samples 15 and 16.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

Verfahren zur Herstellung von verstärkten Vulkanisaten durch Vulkanisation von Natur- oder Kunstkautschuk-Mischungen mit Novolakharzen in Gegenwart einer Aminverbindung als Härter, dadurch gekennzeichnet, daß die Vulkanisation in Gegenwart reaktiver Melaminharze, wie sie durch Umsetzung von Melamin mit 0,5 bis 6 Mol Aldehyd erhalten werden, als Härter in einem Anteil von 0,5 bis 120 Gew.-%, bezogen auf Novolakharz, durchgeführt wird, und daß die phenolische komponente des Novolakharzes aus der Gruppe Phenol, mehrwertige Mehrkernphenole, Alkylphenole, Gemische von Alkylphenolen mit Phenol ausgewählt ist, wobei sie noch Zusätze von Resorcin, Phenylphenol oder Polyalkyl-phenolen enthalten kann, und aus diesen Produkten hergestellte Gummiartikel und Kraftfahrzeugreifen.Process for the preparation of reinforced vulcanizates by vulcanization of natural or synthetic rubber mixtures with novolak resins in the presence of an amine compound as hardener, characterized in that the vulcanization in the presence of reactive melamine resins, as obtained by reacting melamine with 0.5 to 6 mol of aldehyde are carried out as hardeners in a proportion of 0.5 to 120% by weight, based on novolak resin, and in that the phenolic component of the novolak resin is selected from the group phenol, polyvalent multinuclear phenols, alkylphenols, mixtures of alkylphenols with phenol, it may also contain additives of resorcinol, phenylphenol or polyalkylphenols, and rubber articles and automobile tires made from these products.

Description

Es ist bekannt, helle Gummiqualitäten aus natürlichen oder synthetischem Kautschuk durch Vulkanisation mit Schwefel anter Zusatz von mindestens 0,5 %, bezogen auf das Gewicht des Kautschuks, eines härtbaren verätherten Kondensationsproduktes aus Aldehyden und Harnstoff und/oder Melamin, bzw. deren Derivaten herzustellen. Die zur Verstärkung verwendeten Melaminharze können als feste pulverisierte Kondensationsprodukte verwendet werden.It is known to produce light-colored rubber qualities from natural or synthetic rubber by vulcanization with sulfur, with the addition of at least 0.5%, based on the weight of the rubber, of a hardenable etherified condensation product of aldehydes and urea and / or melamine, or their derivatives. The melamine resins used for reinforcement can be used as solid powdered condensation products.

Es ist ebenso bekannt, harte Kautschukvulkanisate durch Vulkanisation von Kautschukmischungen mit Schwefel unter Zusatz von Hexamethoxymethylmelamin oder Harzen, die aus Melamin oder Guanaminen und Aldehyden erhalten und deren Alkylolgruppen durch Alkohole veräthert worden sind, herzustellen. Bei dem zuletzt genannten Verfahren kann die härtende Wirkung durch Zusatz von Polyesterharzen aus Dicarbonsäuren und mehrwertigen Alkoholen, die eine Säurezahl von mindestens 50 aufweisen, intensiviert werden.It is also known to produce hard rubber vulcanizates by vulcanization of rubber mixtures with sulfur with the addition of hexamethoxymethylmelamine or resins which have been obtained from melamine or guanamines and aldehydes and whose alkylol groups have been etherified by alcohols. In the latter process, the hardening effect can be intensified by adding polyester resins made from dicarboxylic acids and polyhydric alcohols which have an acid number of at least 50.

Nach einer weiteren Druckschrift können Gummimischungen aus Natur- oder Synthesekautschuk durch Zusatz von Novlaken und Resolen im Verhältnis 9 : 1 bis 1 : 9 verstärkt werden.According to a further publication, rubber mixtures made of natural or synthetic rubber can be reinforced by adding novlaken and resols in a ratio of 9: 1 to 1: 9.

Die genannten Verfahren sind zwar gemäß den genannten Patentschriften realisierbar und bringen die dort aufgeführten Effekte, haben aber nur begrenzte wirtschaftliche Bedeutung erlangt.Although the methods mentioned can be implemented in accordance with the patents mentioned and bring the effects listed there, they have only limited economic importance.

Praktische Bedeutung hat dagegen die Verstärkung von Gummiqualitäten der verschiedensten Art durch Zusatz von Phenolnovolaken und Hexamethylentetramin als Härtungsmittel. Der verstärkende Effekt der verwendeten Harze kann gegebenenfalls durch die Menge des verwendeten Härtungsmittels wirksam geregelt werden.On the other hand, the strengthening of various types of rubber by adding phenol novolaks and hexamethylenetetramine as curing agents is of practical importance. The reinforcing effect of the resins used can optionally be effectively regulated by the amount of the curing agent used.

Diese in der Praxis bewährte Verstärkung von Gummiqulitäten durch ein Novolakharz und Hexamethylentetramin wird in neu- )erer Zeit aus Gründen des Umweltschutzes kritisch bewertet, weil Hexamethylentetramin die menschliche Haut irritiert und zu Ausschlägen Anlaß geben soll.This tried and tested reinforcement of rubber qualities by a novolak resin and hexamethylenetetramine has recently been critically evaluated for reasons of environmental protection, because hexamethylenetetramine irritates human skin and is said to give rise to rashes.

Es wurde überraschend gefunden, daß zur Verstärkung von Gummi geeignete Novolake der verschiedensten Art durch Zugabe von reaktiven Melaminharzen gehärtet werden, wobei besonders wirkungsvolle Verstärkungseffekte erzielt werden. Gegenstand der Erfindung ist also ein Verfahren zur Herstellung von verstärkten Vulkanisaten durch Vulkanisation Ovon Natur- oder Kunstkautschuk-Mischungen mit Novolakharzen in Gegenwart einer Aminverbindung als Härter, das dadurch gekennzeichnet ist, daß die Vulkanisation in Gegenwart reaktiver Melaminharze, wie sie durch Umsetzung von Melamin mit 0,5 bis 6 Mol Aldehyd erhalten werden, als Härter in Seinem Anteil von 0,5 bis 120, vorzugsweise 2 bis 50 Gew.-%, bezogen auf Novolakharz, durchgeführt wird und daß die phenolische Komponente des Novolakes aus der Gruppe Phenol, mehrwertige Mehrkernphenole, Alkylphenole, Gemische von Alkylphenolen mit Phenol ausgewählt ist, wobei sie noch Zu-Osätze von Resorcin, Phenylphenol oder Polyalkyl-phenolen enthalten kann. Hierbei kennen die Zusätze in einer solchen Menge eingearbeitet werden, daß das Mol-Verhältnis der Gesamt- menge der Zusätze zur Gesamtmenge der anderen Phenole bis 1 : vorteilhaft bis 1 : 2 beträgt,It has surprisingly been found that various novolaks suitable for reinforcing rubber are hardened by adding reactive melamine resins, with particularly effective reinforcing effects being achieved. The invention thus relates to a process for the production of reinforced vulcanizates by vulcanization of natural or synthetic rubber mixtures with novolak resins in the presence of an amine compound as the curing agent, which is characterized in that the vulcanization in the presence of reactive melamine resins, such as those obtained by reacting melamine with 0.5 to 6 moles of aldehyde are obtained as hardeners in a proportion of 0.5 to 120, preferably 2 to 50% by weight, based on novolak resin, and that the phenolic component of the novolak from the phenol group is multivalent Multinuclear phenols, alkylphenols, mixtures of alkylphenols with phenol is selected, which may also contain additions of resorcinol, phenylphenol or polyalkylphenols. The additives are incorporated in such an amount that the molar ratio of the total amount of the additives to the total amount of the other phenols is up to 1: advantageously up to 1: 2,

Die im Melaminharz vorhandenen Methylolgruppen können frei oder zumindest teilweise durch Umsetzung mit einwertigen Alkoholen mit 1 bis 12 C-Atomen veräthert sein.The methylol groups present in the melamine resin can be etherified freely or at least partially by reaction with monohydric alcohols with 1 to 12 carbon atoms.

Melaminharze allein, wie sie gemäß den oben erwähnten bekannten Verfahren verwendet werden könne, haben im Gummimi- schungen der verschiedensten Art eine deutlich schwächere Wirkung als die üblicherweise verwendeten Novolak-Hexamethylentetraminsysteme. Soweit feste,reaktive Melaminharze verwendet werden, hängt deren Effekt in entscheidendem Maße von der Feinheit ihrer Teilchen ab. In der Praxis wird nur in Ausnahmefällen die Teilchengröße von aktiven Füllstoffen erreicht. Auch bei dem erfindungsgemäßen Verfahren können gegebenenfalls feste Melaminharze eingesetzt werden. In der Regel wird man ein Melaminharz mit einer Teilchengröße von höchstens 100 um, vorzugsweise etwa 50 um verwenden. In gelöster Form lassen sich hochreaktive Melaminharze verhältnismäßig leicht herstellen. Harze dieses Typs sind nur bedingt zur Einarbeitung in Kautschuke geeignet, weil die erforderlichen Lösungsmittel wie höhere Alkohole, Wasser, Polyglykole oder Ester mit den meisten Kautschuktypen nicht verträglich sind. Sie müssen im Zuge des Einmischverfahrens verdampft werden. Hexamethoxymethylmelamin selbst ist zwar gut >inarbeitbar, härtet aber nur langsam. Aus diesem Grund hat es nicht den Effekt der praktisch verwendeten Phenolnovolak-Hexamethylentetramin-Gemische.Melamine resins, as they can be used according to known methods mentioned above, alone, have the same grip sc h Ungen of various kinds a much weaker effect than the commonly used novolak Hexamethylentetraminsysteme. If solid, reactive melamine resins are used, their effect depends to a large extent on the fineness of their particles. In practice, the particle size of active fillers is only reached in exceptional cases. Solid melamine resins can optionally also be used in the process according to the invention. Usually a melamine resin with a particle size of at most 100 µm, preferably about 50 µm will be used. In a dissolved form, highly reactive melamine resins are relatively easy to manufacture. Resins of this type are only suitable for incorporation into rubbers to a limited extent because the required solvents such as higher alcohols, water, polyglycols or esters are not compatible with most types of rubbers. They have to be evaporated in the course of the mixing process. Hexamethoxymethylmelamine itself is good> workable, but hardens slowly. For this reason, it does not have the effect of the phenol novolak / hexamethylenetetramine mixtures used in practice.

Hexamethoxymethylmelamin allein reagiert beim Erhitzen nur sehr langsam mit sich selbst. Falls eine Reaktion bei Raumtemperatur gewünscht wird, erfordert die Verwendung dieser Substanz daher den Zusatz starker Säuren, z. B. Salzsäure oder Toluolsulfonsäure. Aus diesem Grund ist es überraschend, daß nach dem erfindungsgemäßen Verfahren die KautschukmiSchungen, denen zur Verstärkung Phenolnovolake der verschiedensten Art zugesetzt wurden, durch Melaminharze der beschriebenen Art, insbesondere Hexamethoxymethylmelamin bzw. die entsprechenden höheren mehrkernigen Kondensationsprodukte der monomeren Melaminharze, sehr energisch gehärtet werden. Es wird sogar vielfach noch ein intensiveτer Verstärkungseffekt als mit Novolak-Hexamethylentetramin-Gemischen erzielt. Die nach dem erfindungsgemäßen Verfahren erzielten Verstärkungseffekte zeigen sich insbesondere in einer Stei- gerung der Spannungswerte bei 100, 200 und 300 % Dehnung sowie in einer Steigerung der Vulkanisathärte.Hexamethoxymethylmelamine alone reacts very slowly with itself when heated. If a reaction at room temperature is desired, the use of this substance therefore requires the addition of strong acids, e.g. B. hydrochloric acid or toluenesulfonic acid. For this reason, it is surprising that, according to the process of the invention, the rubber mixtures to which various kinds of phenol novolaks have been added for reinforcement are cured very vigorously by melamine resins of the type described, in particular hexamethoxymethylmelamine or the corresponding higher multinuclear condensation products of the monomeric melamine resins. In many cases, an intensive reinforcing effect is even achieved than with novolak-hexamethylenetetramine mixtures. Those achieved by the process according to the invention Reinforcement effects are particularly evident in an increase in the tension values at 100, 200 and 300% elongation and in an increase in the vulcanizate hardness.

Bei Anwendung des Verfahrens nach der Erfindung kann die Geschwindigkeit der Harzhärtung und der Härtungseffekt selbst durch Zusatz geeigneter ein- oder zweibasischer organischer Säuren mit mindestens 2 und höchstens 20 C-Atomen bzw. deren Anhydriden, z. B. Phthalsäure, Benzoesäure, Maleinsäure, Fumarsäure, Tri- oder Pyromellithsäure und deren Anhydriden oder Sulfonsäuren wie Naphthalindisulfonsäure oder Sulfanilsäure, wesentlich beschleunigt und intensiviert werden.When using the method according to the invention, the rate of resin curing and the curing effect itself by adding suitable mono- or dibasic organic acids with at least 2 and at most 20 C atoms or their anhydrides, e.g. B. phthalic acid, benzoic acid, maleic acid, fumaric acid, tri- or pyromellitic acid and their anhydrides or sulfonic acids such as naphthalenedisulfonic acid or sulfanilic acid, are significantly accelerated and intensified.

Anstelle von oder zusammen mit den organischen Säuren können auch Polyesterharze aus Polycarbonsäuren und mehrwertigen Alkoholen mit einer Säurezahl von 20 und höher, z. B. bis 100, die auch durch Monocarbonsäuren und einwertigen Alkoholen modifiziert sein können, mitverwendet werden. Der Anteil der einwertigen Komponenten soll jedoch höchstens 25 Äquivalent-%, bezogen auf die Säure- bzw. Alkohol-Komponente, ausmachen.Instead of or together with the organic acids, polyester resins made from polycarboxylic acids and polyhydric alcohols with an acid number of 20 and higher, e.g. B. to 100, which can also be modified by monocarboxylic acids and monohydric alcohols. However, the proportion of monovalent components should not exceed 25 equivalent%, based on the acid or alcohol component.

Die zur Beschleunigung dienenden organischen Säuren bzw. Polyesterharze können in Mengen von 0,1 bis etwa 5, vorzugs-51,5 bis 3 Gew.-%, bezogen auf Kautschuk zugesetzt; werden. Größere oder kleinere Säuredosierungen sind durchaus möglich.The organic acids or polyester resins used for acceleration can be added in amounts of 0.1 to about 5, preferably 51.5 to 3% by weight, based on rubber; will. Larger or smaller acid doses are quite possible.

An sich kann die Beschleunigung der Härtung auch mit Hilfe von starken anorganischen Säuren, wie Phosphorsäure oder sauren Phosphorsäureestern, erreicht werden. Diese Arbeitsweise ist jedoch wegen der im Umgang mit solchen Säuren erforderlichen Vorsichtsmaßnahmen weniger zweckmäßig.As such, the hardening can also be accelerated with the aid of strong inorganic acids, such as phosphoric acid or acidic phosphoric acid esters. However, this method of operation is less expedient because of the precautionary measures required when handling such acids.

Die erfindungsgemäß eingesetzten Ausgangsmischungen können 5in üblicher Weise in Innenmischern oder auf Mischwalzen hergestellt werden. Beim Einarbeiten der Harze ist darauf zu achten, daß die Mischungstemperatur in irgendeiner Phase der Mischungsherstellung den Schmelzpunkt der Harze, insbesondere der Novolakharze überschreitet, damit sich diese völlig verteilen können Ferner ist wichtig, daß die als iärtungsmittel zu verwendenden Melaminharze so eingearbeitet werden, daß es nicht zu einer vorzeitigen Eigenkondensation oder zu einer vorzeitigen Reaktion mit dem zu därtenden Novolak kommt. Das ist möglich, wenn die Melaminnarze am Ende des Mischvorganges bei nicht zu hohen Temberaturen eingearbeitet werden. Die Temperatur richtet sich nach dem jeweils verwendeten Melaminharztyp, der Säuremenge und der Zeit und liegt im allgemeinen bei 80° bis 120°C. in Einzelfällen kann sie auch höher - z. B. bei Verwendung von Hexamethoxymethylmelamin in Abwesenheit einer Säure - oder auch tiefer sein.The starting mixtures used according to the invention can be produced in the usual way in internal mixers or on mixing rollers. When incorporating the resins, care must be taken to ensure that the mixing temperature in any phase of the Mixing exceeds the melting point of the resins, especially the novolak resins, so that they can be completely distributed. It is also important that the melamine resins to be used as curing agents are incorporated in such a way that there is no premature self-condensation or premature reaction with the novolak to be cured . This is possible if the melamine resins are incorporated at the end of the mixing process if the temperature is not too high. The temperature depends on the type of melamine resin used, the amount of acid and the time and is generally from 80 ° to 120 ° C. in individual cases it can also be higher - e.g. B. when using hexamethoxymethylmelamine in the absence of an acid - or lower.

Geeignete Kautschuktypen sind beispielsweise Naturkautschuk, Styrolkautschuk, Acrylnitrilkautschuk, Polybutadien, Butylkautschuk, Äthylen-Propylen-Dien-Terpolymer-Kautschuk oder deren Gemische, wie sie üblicherweise in der Reifenindustrie oder zur Herstellung technischer Gummiwaren verwendet werden.Suitable types of rubber are, for example, natural rubber, styrene rubber, acrylonitrile rubber, polybutadiene, butyl rubber, ethylene-propylene-diene terpolymer rubber or mixtures thereof, as are usually used in the tire industry or for the production of technical rubber products.

Geeignete Novolak-Harze sind z. B. solche, die aus Phenol, mehrwertigen Mehrkernphenolen, wie Bisphenolen, z. B. Diphenylolpropan oder Diphenylolmethan, oder Gemischen aus Phenol und Alkylphenolen, wie tertiär-Butylphenol, Octylphenol oder Nonylphenol und Aldehyden, vorzugsweise Formaldehyd im sauren Gebiet erhalten werden. Die Novolak-Harze können außerdem weichmachende Anteile, wie Polyäthylenglykole, Tallöl oder andere geeignete Plastifiziermittel erhalten. Grundsätzlich können auch Novolak-Harze, die ausschließlich aus Alkylphenolen, die eine Alkylgruppe von 1 bis 12 C-Atomen tragen, verwendet werden; diese kommen jedoch nur bedingt in Frage, da sie weniger härtbar sind. Ferner können die Novolak-Harze Zusätze von Resorcin oder Phenylphenol oder mehrere Alkylgruppen enthaltenden Phenolen enthalten. Für den praktischen Gebrauch sind Novolak-Harze aus Phenol und Gemischen aus Phenol und Cashew-Nußschalenöl sowie aus Phenol und Alkylphenolen mit 4 bis 12 C-Atomcn im Alkylteil, insbesondere p-tert.Butyl-, Octyl- oder Nonylphenol bevorzugt. Der Anteil der substituierten Phenole im Novolak kann dabei variieren, wobei jedoch der Novolak noch härtbar sein soll. So wird man im allgemeinen einen Anteil an Alkylphenol von höchstens 70 Mol-% der gesamten Phenolkomponente wählen.Suitable novolak resins are e.g. B. those made of phenol, polyvalent multinuclear phenols such as bisphenols, e.g. B. diphenylolpropane or diphenylolmethane, or mixtures of phenol and alkylphenols, such as tertiary-butylphenol, octylphenol or nonylphenol and aldehydes, preferably formaldehyde in the acidic region. The novolak resins can also contain plasticizing components, such as polyethylene glycols, tall oil or other suitable plasticizers. In principle, novolak resins can also be used which consist exclusively of alkylphenols which carry an alkyl group of 1 to 12 carbon atoms; however, these are only of limited use since they are less hardenable. Furthermore, the novolak resins can contain additions of resorcinol or phenylphenol or phenols containing several alkyl groups. For the practical use are preferred novolak resins from phenol and mixtures of phenol and cashew nutshell oil and from phenol and alkylphenols with 4 to 12 carbon atoms in the alkyl part, in particular p-tert-butyl, octyl or nonylphenol. The proportion of substituted phenols in the novolak can vary, although the novolak should still be curable. In general, a proportion of alkylphenol of at most 70 mol% of the total phenol component will be chosen.

Der Anteil des Novolaks beträgt in der Regel 1 bis 30, vorzugsweise 3 bis 20 Gew.-%, bezogen auf das Elastomere. In Einzelfällen lassen sich auch größere Mengen, z. B. 100 und mehr Gew.-%, bezogen auf das Elastomere, verwenden. Bei einem derart hohen Novolakanteil erhält man harte Produkte, die sich in ihren Eigenschaften wesentlich von den üblichen hochelastischen Kautschukvulkanisaten unterscheiden.The proportion of the novolak is generally 1 to 30, preferably 3 to 20% by weight, based on the elastomer. In individual cases, larger quantities, e.g. B. Use 100 and more wt .-%, based on the elastomer. With such a high novolak content, hard products are obtained which differ significantly in their properties from the usual highly elastic rubber vulcanizates.

Bevorzugte Melaminharze sind Hexamethoxymethylmelamin oder entsprechende höherkondensierte mehrkernige Produkte oder zumindest teilweise verätherte Trimethylol-, Tetramethylol-, oder Pentamethylol- Melaminharze. Der Kondensationsgrad der Aldehyd-, insbesondere Formaldehyd-Harze und ihr Gehalt an freien Methylolgruppen kann in üblicher Weise durch entsprechende Einstellung des Reaktionsmediums geregelt werden. Die freien Methylolgruppen können mit einwertigen Alkoholen mit 1 bis 12, vorzugsweise 1 bis 8 C-Atomen veräthert sein, wie Methanol, den verschiedenen Butanolen, Äthylhexylalkohol, n-Octanol, Nonanol, Dodecylalkohol.Preferred melamine resins are hexamethoxymethylmelamine or corresponding higher condensed polynuclear products or at least partially etherified trimethylol, tetramethylol or pentamethylol melamine resins. The degree of condensation of the aldehyde, especially formaldehyde resins and their content of free methylol groups can be regulated in the usual way by appropriate adjustment of the reaction medium. The free methylol groups can be etherified with monohydric alcohols having 1 to 12, preferably 1 to 8, carbon atoms, such as methanol, the various butanols, ethylhexyl alcohol, n-octanol, nonanol, dodecyl alcohol.

Die zur Härtung der Novolak-Harze erforderlichen optimalen Mengen Melaminharze müssen im Prinzip in Vorversuchen, die einfach durchzuführen sind, ermittelt werden. Im allgemeinen sind auf 100 Gewichtsteile Novolak-Harz etwa 1 bis 80, vorzugsweise 2 bis 50 Gew.-% Melaminharz erforderlich.In principle, the optimum amounts of melamine resins required for curing the novolak resins must be determined in preliminary tests which are easy to carry out. In general, about 1 to 80, preferably 2 to 50% by weight of melamine resin is required per 100 parts by weight of novolak resin.

Es ist auch möglich, anstelle von oder zusammen mit den Säuren auch Weichmacher, wie sie bei der Kautschukverarbeitung üblich sind, zuzugeben, beispielsweise aromatische Polyäther, Phthalsäureester oder dergleichen.Instead of or together with the acids, it is also possible to add plasticizers, as are customary in rubber processing, for example aromatic polyethers, phthalic acid esters or the like.

Als Füllstoffe können die handelsüblichen aktiven oder inaktiven Ruße, Kieselsäuren, Kaoline, Kreide oder andere übliche Füllstoffe mitverwendet werden. Zur Vulkanisation wird in der Regel Schwefel in Zusammenhang mit den allseits bekannten Beschleunigern verwendet. In manchen Fällen kann jedoch auch ohne Schwefel gearbeitet werden. Die Vulkanisation in Gegenwart von Schwefel ist aber bevorzugt. Der Vulkanisationsverlauf kann durch Auswahl geeigneter in der Kautschuktechnologie üblicher Beschleuniger den praktischen Erfordernissen angepaßt werden.The commercially available active or inactive carbon blacks, silicas, kaolins, chalk or other customary fillers can also be used as fillers. As a rule, sulfur is used for vulcanization in connection with the well-known accelerators. In some cases, however, it is also possible to work without sulfur. Vulcanization in the presence of sulfur is preferred. The course of vulcanization can be adapted to practical requirements by selecting suitable accelerators which are customary in rubber technology.

Aus den nach der Erfindung hergestellten, ein Novolak-Harz und ein Melaminharz enthaltenden Mischungen können technische Gummiartikel hergestellt werden; sie können aber auch )für die Herstellung von Kraftfahrzeugreifen verwendet werden.Technical rubber articles can be produced from the mixtures produced according to the invention and containing a novolak resin and a melamine resin; but they can also be used for the manufacture of motor vehicle tires.

In den nachstehenden Beispielen bedeuten die Mengenangaben GT = Gewichtsteile.

Figure imgb0001
In the examples below, the amounts given are GT = parts by weight.
Figure imgb0001

Diskussion der Ergebnisse von Tabelle 1Discussion of the results from Table 1

Die Mischungen V 1 und V 2 sind Vergleichsmischungen. Mischung V 2 zeigt die Verstärkung einer Styrol-Butadien- Ruß-Mischung mit einem handelsüblichen Phenolnovolak bei Härtung mit Hexamethylentetramin. Mischung 1 zeigt den Verstärkungseffekt nach der Erfindung bei Verwendung einer handelsüblichen, wasser- und lösemittelfreien, höherviskos eingestellten Hexamethoxymelaminqualität. Mischung 2 zeigt den Effekt der zur Beschleunigung der Härtung mitverwendeten Benzoesäure.The mixtures V 1 and V 2 are comparative mixtures. Mixture V 2 shows the reinforcement of a styrene-butadiene R USS mixture with a commercially available phenol novolak when cured with hexamethylenetetramine. Mixture 1 shows the reinforcing effect according to the invention when using a commercially available, water- and solvent-free, higher-viscosity hexamethoxymelamine quality. Mixture 2 shows the effect of the benzoic acid used to accelerate curing.

Die Vulkanisate der Mischung V 2 zeichnen sich gegenüber Mischung V 1 durch einen etwas höheren Spannungswert bei 100 % und deutlich höhere Vulkanisathärte aus. Die nach der Erfindung hergestellte Mischung 1 gibt Vulkanisate mit einem weiter erhöhten Spannungswcrt bei 100'% Dehnung und deutlich höherer Härte. Durch die Mitverwendung von Benzoesäure werden die Spannungswerte bei 100, 200 und 300 % Dehnung und die Vulkanisathärte zusätzlich erhöht.The vulcanizates of the mixture V 2 are distinguished from mixture V 1 by a somewhat higher voltage value at 100% and significantly higher vulcanizate hardness. The mixture 1 produced according to the invention gives vulcanizates with a further increased tension value at 100% elongation and significantly higher hardness. By using benzoic acid, the tension values at 100, 200 and 300% elongation and the vulcanizate hardness are additionally increased.

Wird anstelle des hochviskosen Hexamethoxymethylmelamins eine niedrigerviskose Qualität (4000 - 8000 mPa.s) verwendet, können Vulkanisathärten über 90 Shore A erhalten werden.If a low-viscosity grade (4000 - 8000 mPa.s) is used instead of the highly viscous hexamethoxymethylmelamine, vulcanizate hardness over 90 Shore A can be obtained.

Werden anstelle der 6 Gew.-Teile Hexamethoxymethylmelamin 6 Gew.-Teile eines pulverförmigen Melaminharzes, das durch Umsetzung von 1 Mol Melamin mit ca. 1,2 Mol Formaldehyd 5 erhalten wurde, verwendet, so werden Vulkanisate erhalten, die in ihren Prüfdaten den Vulkanisaten der Mischung 1 weitgehend entsprechen.If instead of the 6 parts by weight of hexamethoxymethylmelamine, 6 parts by weight of a powdered melamine resin obtained by reacting 1 mol of melamine with approx. 1.2 mol of formaldehyde 5 are used, vulcanizates are obtained which, in their test data, are the vulcanizates largely correspond to mixture 1.

Die nach der Erfindung hergestellten Mischungen 3 und 4 zeigen, daß plastifizierende Zusätze, wie Diäthylenglykol oder ein saures Phthalsäure-Pentaerythrit-Polyesterharz, mit Vorteil mitverwendet werden können. Durch das Diäthylenglykol wird die Mooney-Viskosität um ca. 10-15 Einheiten gegenüber einer Vergleichsmischung herabgesetzt. Das in Mischung 4 zugesetzte Polyesterharz mit der Säurezahl von ca. 200 begünstigt die Härtungsreaktion.

Figure imgb0002
Figure imgb0003
Figure imgb0004
 Mixtures 3 and 4 produced according to the invention show that plasticizing additives, such as diethylene glycol or an acidic phthalic acid pentaerythritol polyester resin, can be used with advantage. The diethylene glycol reduces the Mooney viscosity by approx. 10-15 units compared to a comparison mixture. The polyester resin with an acid number of approx. 200 added to mixture 4 favors the curing reaction.
Figure imgb0002
Figure imgb0003
Figure imgb0004

In den Tabellen 2 bis 4 wurden jeweils derselbe Kautschuk und derselbe Ruß wie nach Tabelle 1 verwendet.Tables 2 to 4 used the same rubber and carbon black as in Table 1.

Diskussion der Ergebnisse von Tabellen 2 bis 4Discussion of the results from Tables 2 to 4

Die Mischungen V5 und V12 sind Vergleichsmischungen. Wie der Vergleich der Härte und der Spannungswerte der erfindungsgemäßen Mischungen 6 bis 8 in Tabelle 2 mit den entsprechenden Werten der Vergleichsprobe V5 zeigt, sind die Härte- und die Spannungswerte gegenüber denjenigen der Ver- gleichsprobe angestiegen. Die Mischungen 9 bis 11 zeigen noch eine stärkere Erhöhung der Härte und der Spannung, die vermutlich durch die kombinierte Wirkung der beiden Melaminharze bedingt ist.Mixtures V5 and V12 are comparative mixtures. As the comparison of the hardness and the tension values of the mixtures 6 to 8 according to the invention in Table 2 shows with the corresponding values of the comparison sample V5, these are Hardness and the voltage values from those of the encryption g l calibration sample increased. Mixtures 9 to 11 show an even greater increase in hardness and tension, which is presumably due to the combined action of the two melamine resins.

In Tabelle 3 zeigen die erfindungsgemäßen Mischungen 13 und 14 gegenüber der Vergleichsprobe V12 ebenfalls eine deutliche Verbesserung der Härte und des Spannungswertes. Die höhere Härte ist vermutlich auf das andere Beschleunigersystem zurückzuführen.In Table 3, mixtures 13 and 14 according to the invention also show a significant improvement in hardness and stress value compared to comparative sample V12. The higher hardness is probably due to the other accelerator system.

Tabelle 4 läßt bei beiden Proben 15 und 16 ein verstärktes Vulkanisat mit guten Spannungswerten und hoher Härte erkennen.Table 4 shows an increased vulcanizate with good tension values and high hardness in both samples 15 and 16.

Claims (10)

1) Verfahren zur Herstellung von verstärkten Vulkanisaten durch Vulkanisation von Natur- oder Kunstkautschuk-Mischungen mit Novolakharzen in Gegenwart einer Aminverbindung als Härter, dadurch gekennzeichnet, daß die Vulkanisation in Gegenwart reaktiver Melaminharze, wie sie durch Umsetzung von 1 Mol Melamin mit 0,5 bis 6 Mol Aldehyd erhalten werden, als Härter in einen: Anteil von 0,5 bis 120 Gew.-%, bezogen auf Novolakharz, durchgeführt wird, und daß die phenolische Komponente des Novclakharzes aus der Gruppe Phenol, mehrwertige Mehrkernphenole, Alkylphenole, Gemische von Alkylphenolen mit Phenol ausgewählt ist, wobei sie noch Zusätze von Resorcin, Phenylphenol oder Polyalkyl-phenolen enthalten kann.1) Process for the preparation of reinforced vulcanizates by vulcanization of natural or synthetic rubber mixtures with novolak resins in the presence of an amine compound as hardener, characterized in that the vulcanization in the presence of reactive melamine resins, such as those obtained by reacting 1 mol of melamine with 0.5 to 6 moles of aldehyde are obtained as a hardener in a: proportion of 0.5 to 120 wt .-%, based on novolak resin, and that the phenolic component of the Novclak resin from the group phenol, polyvalent multinuclear phenols, alkylphenols, mixtures of alkylphenols is selected with phenol, which may also contain additions of resorcinol, phenylphenol or polyalkylphenols. 2) Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß solche Melaminharze eingesetzt werden, deren Methylolgruppen, zumindest teilweise mit einwertigen Alkoholen mit 1 bis 12, vorzugsweise bis 8 C-Atomen veräthert sind.2) Method according to claim 1, characterized in that such melamine resins are used, the methylol groups, at least partially etherified with monohydric alcohols having 1 to 12, preferably up to 8 carbon atoms. 3) Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Umsetzung in Gegenwart von Melaminharz in einem Anteil von 1 bis 80, vorzugsweise 2 bis 50 Gew.-% durchgeführt wird.3) Method according to claim 1 or 2, characterized in that the reaction is carried out in the presence of melamine resin in a proportion of 1 to 80, preferably 2 to 50 wt .-%. 4) Verfahren nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Vulkanisation in Gegenwart von anorganischen oder ein- oder zweibasischen organischen Säurenkemponenten mit 2 bis 20 C-Atomen und /oder Polyestern mit einer Säurezahl von mindestens 20 durchgeführt wird.4) Method according to one or more of claims 1 to 3, characterized in that the vulcanization is carried out in the presence of inorganic or mono- or dibasic organic acid components with 2 to 20 carbon atoms and / or polyesters with an acid number of at least 20. 5) Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Anteil der organischen Säurekomponente 0,1 bis 5 Gew.-%, bezogen auf Kautschuk,beträgt.5) Method according to one or more of claims 1 to 4, characterized in that the proportion of the organic acid component is 0.1 to 5 wt .-%, based on rubber. 6) Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, 5dadurch gekennzeichnet, daß solche Kautschuk-Mischungen vulkanisiert werden, in die der Novolak und das Melaminharz wenigstens teilweise bei einer Temperatur oberhalb des Schmelzpunktes der Novolakharze, vorzugsweise von 80 bis 120°C eingemischt worden sind.6) Method according to one or more of claims 1 to 5, 5 characterized in that such rubber mixtures vul can be cannulated into which the novolak and the melamine resin have been mixed at least partially at a temperature above the melting point of the novolak resins, preferably from 80 to 120 ° C. 7) Verfahren nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß Mischungen vulkanisiert werden, die einen Phenol-p-tert.-Butylphenol-, einen Phenol-Octylphenol-, einen Phenol-Nonylphenol-Novclak und/oder einen Novolak aus Phenol und Cashew-Nußschalenöl enthalten.7) Method according to one or more of claims 1 to 6, characterized in that mixtures are vulcanized, a phenol-p-tert-butylphenol, a phenol-octylphenol, a phenol-nonylphenol-Novclak and / or a novolak from phenol and cashew nutshell oil. 8) Verfahren nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß Mischungen vulkanisiert werden, in denen die gesamte Phenolkomponente des Novolaks. einen Anteil an Alkylphenol von höchstens 70 Mol-% enthält.8) Method according to one or more of claims 1 to 7, characterized in that mixtures are vulcanized in which the entire phenol component of the novolak. contains a proportion of alkylphenol of at most 70 mol%. 9) Verfahren nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß Mischungen vulkanisiert werden, deren Novolak-Anteil 1 bis 30, vorzugsweise 3 bis 20 Gew.-%, bezogen auf Kautschuk, ausmacht.9) The method according to one or more of claims 1 to 8, characterized in that mixtures are vulcanized, the novolak content of 1 to 30, preferably 3 to 20 wt .-%, based on rubber. 10) Gummiartikel und Kraftfahrzeugreifen, hergestellt nach dem Verfahren eines oder meheren der Ansprüche 1 bis 9.10) rubber articles and motor vehicle tires manufactured by the method of one or more of claims 1 to 9.
EP79104787A 1978-12-04 1979-11-30 Process for preparing reinforced rubber vulcanisates and the articles thus obtained Expired EP0013330B1 (en)

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EP0036515B1 (en) * 1980-03-15 1984-10-31 Hoechst Aktiengesellschaft Process for the preparation of reinforced vulcanised-rubber compositions
US4542186A (en) * 1980-03-15 1985-09-17 Hoechst Aktiengesellschaft Process for the preparation of reinforced rubber vulcanisates and the use thereof
EP0090387A2 (en) * 1982-03-31 1983-10-05 Aktiengesellschaft Hoechst Rubber vulcanisates with low hardness, process for preparing rubber vulcanisates having a Shore A hardness less than 65 degrees, characterized by a reduced transformation of heat energy during dynamic deformation, and commercial rubber compositions and tyres
EP0090387A3 (en) * 1982-03-31 1984-02-22 Aktiengesellschaft Hoechst Rubber vulcanisates with low hardness, process for preparing rubber vulcanisates having a shore a hardness less than 65 degrees, characterized by a reduced transformation of heat energy during dynamic deformation, and commercial rubber compositions and tyres
FR2693467A1 (en) * 1992-07-08 1994-01-14 Michelin & Cie Process and composition for the use of substituted melamines as novolak resin hardeners
WO1994001493A1 (en) * 1992-07-08 1994-01-20 Compagnie Generale Des Etablissements Michelin - Michelin & Cie Method and composition for using substituted melamines as novolak resin curing agents
US6686418B2 (en) 2000-07-14 2004-02-03 Solutia Germany Gmbh & Co. Kg Rubber products with low heat build up on mechanical stressing

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Publication number Publication date
PT70536A (en) 1980-01-01
ATE5194T1 (en) 1983-11-15
CA1152687A (en) 1983-08-23
JPS5578034A (en) 1980-06-12
ES486394A1 (en) 1980-05-16
EP0013330B1 (en) 1983-11-02
DE2966380D1 (en) 1983-12-08
DE2852311C2 (en) 1981-04-09
DE2852311B1 (en) 1980-06-12
DK513579A (en) 1980-06-05
US4465807A (en) 1984-08-14

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